Chemical Physics · Cross-listed from q-bio.BM
New water oxidation mechanism in Photosystem II resolves major experimental controversies
Yulia Pushkar
Light driven oxygen formation in Photosystem II
protein is a fundamental process that sustains our biosphere and serves as a blue print to future clean energy solutions due to its high energy conversion efficiency. Last decade of intense research by advanced physical techniques delivered new insights on the structure and function of the Mn4CaO5 cluster a center of the oxygen evolving complex (OEC). However, discrepancies in experimental observations and computational models persist impeding the understanding of the O-O bond formation and the role of the
protein environment in the process. Here we show that i) assignment of the OEC unique oxygen O3 ligated by histidine (His337) via dynamic H-bond as a slow exchanging substrate and ii) its coupling with O6 oxygen generated at Mn1 in the S2 to S3 transition give the O-O bond formation mechanism most consistent with all currently available experimental data. Proposal shows how
protein environment can steer the O-O bond formation by charge control via H-bond and open coordination of Mn1. Obtained O3-O6 peroxide is at lower energy than peroxides in the most studied O5-O6 bond formation pathway. His337 appears to be similar to distal His in globins used for management of the O2 and H2O2 intermediates. The new mechanism breaks the prior impasse and will undoubtedly invigorate future detailed studies uncovering its further details.
Read the full abstract ▾
Computational Physics
Level set-based topology optimization of micropolar solids under thermo-mechanical loading
Mayank Shekhar, Ayyappan Unnikrishna Pillai, Subhayan De et al. (+1 more)
We propose a novel level set-based
topology optimization for micropolar solids subjected to thermo-mechanical loading. To capture the size effects, we have incorporated the microstructural length-scale information into the level set-based
topology optimization method by adopting a micropolar theory. The proposed non-local
topology optimization method can provide accurate
topology optimization for size-dependent solids under thermo-mechanical loading. We have demonstrated the effectiveness of the proposed method through a few representative two-dimensional
benchmark problems. The numerical results reveal the substantial influence of underlying micro-structures, incorporated in the model through micropolar parameters, and temperature on
topology optimization, highlighting the necessity of the proposed thermo-mechanical micropolar formulation for materials with pronounced non-local effects. For the numerical implementation of the proposed model, we have used open-source finite element libraries, Gridap.jl, and GridapTopOpt.jl, available in Julia, to ensure transparency and reproducibility of the reported computational results.
Read the full abstract ▾
All authors Mayank Shekhar, Ayyappan Unnikrishna Pillai, Subhayan De, Mohammad Masiur Rahaman
Fluid Dynamics
Lagrangian Phase-Lag and Geometric Precedence in Turbulent Vortex Stretching
Khalid Saqr
This study investigates the causal timeline of
vortex stretching in high-Reynolds-number
turbulence ($Re_\lambda \approx 433$) using Lagrangian tracking in $1024^3$ direct numerical simulations. While classical theories often assume an instantaneous
alignment between strain and vorticity, the present analysis identifies a systematic Lagrangian phase lag governing the onset of intense dissipation. By conditionally averaging the dynamics of fluid parcels, a distinct phase-space hysteresis is revealed. Trajectories are captured by the saddle-point
topology of the pressure field ($\lambda_{min}^p < 0$) prior to experiencing peak enstrophy amplification. This temporal ordering ($\tau > 0$) demonstrates that the pressure
topology acts as a deterministic
geometric precursor, organizing the flow structure before the bursting event occurs. The robustness of this mechanism is verified in magnetohydrodynamic (MHD)
turbulence, where the Lorentz force is found to suppress the hysteresis loop, forcing a transition from causal precedence to simultaneous locking.
Read the full abstract ▾
Fluid Dynamics
Assessment of the Rankine Vortex Model for Modeling the Gas Entrainment in a Representative Mock-up of a Sodium Fast Reactor
David Guenadou, Philippe Aubert and Jean-Philippe Descamps
Since decades, the CEA has been involved in the development of 4th generation reactors cooled by sodium. The dedicated experimental platform PLATEAU was erected to study the different issues and built a results database for the code validation. As experiments with sodium are complex, the tests are led in mock-ups using water as a simulant fluid. The MICAS mock-up, model of the upper plenum, aims at studying the gas entrainment at the free surface. Gas is prohibited in the reactor core due to
neutron effects, which may induce reactivity variations. Since
vortices are difficult to handle by numerical codes in complex geometries such as reactor ones, criteria have been developed based on the Rankine
vortex model to forecast the air entrainment. However, in some case, numerical results do not correlate the experimental ones and those discrepancies are may be due to the
vortex model. This article aims at comparing the
vortices characteristics calculated using the Rankine
vortex model with experimental results in order to improve the gas entrainment criteria. The parameters of the Rankine model are determined using the velocity fields measured by the Particle Image Velocity (PIV) method and the
vortices diameter is calculated using the raw PIV images.
Read the full abstract ▾
Instrumentation and Detectors
Differentiable Surrogate for Detector Simulation and Design with Diffusion Models
Xuan Tung Nguyen, Long Chen, Tommaso Dorigo et al. (+7 more)
In this work, we present a conditional denoising-
diffusion surrogate for electromagnetic calorimeter showers that is trained to generate high-fidelity energy-deposition maps conditioned on key detector and beam parameters. The model employs efficient inference using Denoising
Diffusion Implicit Model sampling and is pre-trained on GEANT4 simulations before being adapted to a new calorimeter geometry through Low-Rank Adaptation, requiring only a small post-training
dataset. We evaluate physically meaningful observables, including total deposited energy, energy-weighted radius, and shower dispersion, obtaining relative root mean square error values below 2% for representative high-energy cases. This is in line with state-of-the-art calorimeter surrogates which report comparable fidelity on high-level observables. Furthermore, we compare gradients of a reconstruction-based utility function with respect to design parameters between the surrogate and finite-difference references. The
diffusion surrogate reproduces the qualitative structure and directional trends of the true utility landscape, providing usable sensitivities for gradient-based optimization. These results show that
diffusion-based surrogates can accelerate simulation-driven detector design while enabling differentiable, gradient-informed analysis.
Read the full abstract ▾
All authors Xuan Tung Nguyen, Long Chen, Tommaso Dorigo, Nicolas R. Gauger, Pietro Vischia, Federico Nardi, Muhammad Awais, Hamza Hanif, Shahzaib Abbas, Rukshak Kapoor
General Physics
Electroweak Structure and Three Fermion Generations in Clifford Algebra with S3 Family Symmetry
Niels Gresnigt
We construct an explicit algebraic realisation of three
fermion generations within a single Clifford
algebra, transforming under the full Standard Model $SU(3)_C\times SU(2)_L\times U(1)_Y$ gauge group, in which an intrinsic $S_3$ family
symmetry permutes three algebraically distinguished but gauge-equivalent
fermion sectors without replicating the gauge
bosons. Fermionic states are represented by minimal left ideals of the complex Clifford
algebra $\mathbb{C}\ell(10)$, while the three-generation structure arises from an embedded discrete $S_3$
symmetry acting on the space of algebraic spinors. The Standard Model gauge generators are identified as elements commuting with this $S_3$ action and act on physical states via the adjoint (commutator) action. The resulting spectrum reproduces the correct Standard Model
quantum numbers for three linearly independent generations of
fermions.
Read the full abstract ▾
History and Philosophy of Physics · Cross-listed from gr-qc
On Causality and Predictivity
Damiano Anselmi
Certain approaches to
quantum gravity, such as the one based on the concept of purely virtual particles (fakeons), sacrifice the cause-effect relation at very small scales to reconcile renormalizability with unitarity. Other developments have also urged caution regarding the idea of causality as a fundamental principle. In this paper, we examine the problem from multiple perspectives, including locality and predictivity, and extend the existing skepticism in several directions. Emphasizing the impact of unruly "disruptors", we point out that the illusory arrow of time associated with causality and predictivity is inherently statistical. This renders the cause-effect relation strained at the microscopic level. We also show that causation is a borderline concept that demands belief in entities which can act on nature without being part of it. Ultimately, not only is renouncing microcausality a reasonable price to pay for a consistent and predictive theory of
quantum gravity (as is the one based on the fakeon idea), but the very notion of causality is misleading. Resting as it does on metaphysical assumptions, it should therefore be abandoned in fundamental physics.
Read the full abstract ▾
Atomic Physics
Controlling Rydberg atom-polariton interactions: from exceptional points to fast readout
Tamara Šumarac, Emily H. Qiu, Shai Tsesses et al. (+8 more)
Rydberg atoms represent a platform underpinning many recent developments in
quantum computation, simulation, sensing, and metrology. They further facilitate optical nonlinearity at the single-
photon level when coupled to
photons propagating in atomic clouds, which form collective atomic excitations called Rydberg polaritons, strongly interacting with each other. Here, we experimentally explore interactions between a Rydberg polariton in an atomic ensemble and a single, adjacent, Rydberg atom. We discover three different regimes of
quantum dynamics corresponding to polariton blockade, coherent exchange, and probabilistic hopping, which are defined by their distinct transmission characteristics, with a transition through an exceptional point occurring between blockade and coherent exchange. We investigate the applications of such interactions for fast, non-destructive detection of Rydberg atoms and present proof-of-principle demonstrations for their potential application in nonlinear photonic networks.
Read the full abstract ▾
All authors Tamara Šumarac, Emily H. Qiu, Shai Tsesses, Peiran Niu, Adrian J. Menssen, Wenchao Xu, Valentin Walther, Uroš Delić, Soonwon Choi, Mikhail D. Lukin, Vladan Vuletić
Optics
Simulation package for solving dynamic diffraction problems in deformed crystals. Bragg, Laue geometry, asymmetric reflections, bend crystals, dislocations, crystals with arbitrary shapes, strain distributions and time dependent problems
Jacek Krzywinski and Aliaksei Halavanau
We demonstrate the use of the Fast
Fourier Transform Beam Propagation Method (FFT BPM) to simulate dynamic diffraction effects, including scattering from deformed
crystals with arbitrary shapes in Bragg, Laue, and asymmetric geometries. The method's straightforward
algorithm, combined with FFT, enables fast computation and is easy to implement in Python. It successfully reproduces literature results for bent
crystals, dislocations, and finite-shaped
crystals simulated using the Takagi-Taupin equations. Python implementations for each case are provided in a public GitHub repository, with the code structured for parallel computing.
Read the full abstract ▾
Applied Physics
Hierarchical metamaterials with tunable flat bands, zero-frequency, and wavenumber gaps
Mohamed A. Elgamal and Osama R. Bilal
Metamaterials are arrangement of basic building blocks that repeat in space, time, or both. These material systems serve as an excellent platform for controlling waves, such as engineering wavenumber band gaps, flat bands, and zero-frequency band gaps. However, combining one or more of these exotic features within the same unit
cell design remains a challenge. Moreover, once a metamaterial is realized, its dispersive properties are usually fixed. In this work, we present a tunable passive hierarchical metamaterial capable of exhibiting wavenumber band gaps, flat bands, and zero-frequency band gaps within the same dispersion curve. Our metamaterial is composed of
magnetic elements confined within a fixed
magnetic boundary. The metamaterial can be tuned by adjusting the
magnetic boundary, which in turn can alter the
lattice periodicity. We open wavenumber band gaps by incorporating
magnetic coupling within the unit
cell elements, resulting in negative physical stiffness. The tunability of the
magnetic coupling also enables complete flattening of the dispersion bands. Moreover, the ground stiffness within our unit-
cell design causes the opening of zero-frequency band gaps. We present our approach through a combination of analytical, numerical, and experimental methods. The analytical framework provides a blueprint for obtaining each of these exotic dispersion characteristics. The numerical analysis, using both linear and nonlinear models, validates our analytical predictions, which we further confirm through experimental demonstrations. Our work opens the door to exploring
magnetic tunability and hierarchy in engineering metamaterial systems with exotic properties that can be harnessed in advanced acoustic and mechanical devices.
Read the full abstract ▾
Geophysics · Cross-listed from cs.LG
Sensoformer: Robust Sim-to-Real Inference on Variable-Geometry Sensor Sets via Physics-Structured Randomization
Zhe Jia, Xiaotian Zhang and Junpeng Li
Inferring high-dimensional physical states from sparse, ad-hoc sensor arrays is a fundamental challenge across AI for Science and industrial IoT. Standard machine learning architectures struggle in these domains due to irregular, variable-cardinality sensor geometries and the profound sim-to-real distribution shift caused by unmodeled physical heterogeneities. To address these challenges, we propose Sensoformer, a set-
attention framework integrated with Physics-Structured Domain Randomization (PSDR). By explicitly randomizing the underlying physical dynamics (e.g., propagation media, extreme noise, and network availability dropout) rather than just visual features, PSDR enforces the learning of domain-invariant physical operators. Using seismic source inversion as a rigorous real-world testbed, Sensoformer is pre-trained on 100,000 synthetics and evaluated on a highly complex real-world catalog. We demonstrate that Sensoformer achieves state-of-the-art precision and outperforms Message Passing Neural Networks (MPNNs) and Neural Operators (e.g., DeepONet) which struggle with extreme spatial sparsity and mixed-modality inputs. Furthermore, interpretability analysis reveals that the
attention mechanism autonomously discovers optimal experimental design principles, dynamically prioritizing sparse orthogonal sensors to overcome information bottlenecks.
Read the full abstract ▾
Atomic Physics
Creation and precise spectroscopy of $^{86}$Sr$_2$ halo molecules
Brandon Iritani, Jingjing Huang, Wenwei Xu et al. (+3 more)
We report on the creation of $^{86}$Sr$_2$ molecules in the
halo state and neighboring weakly bound states. Efficient molecule production via one-
photon photoassociation relies on sufficient wavefunction overlap between the target vibrational states in the electronic excited- and ground-state potentials. Using Autler-Townes spectroscopy, transition strengths are measured to identify optimal pathways for production of weakly bound molecules. Vibrational splittings for the three least-bound vibrational states are measured, and dominant systematic uncertainties are evaluated with uncertainties below 100 Hz. From these splittings, absolute binding energies for these weakly bound vibrational states are determined. The results pave the way to a molecular isotope shift measurement with Sr$_2$.
Read the full abstract ▾
All authors Brandon Iritani, Jingjing Huang, Wenwei Xu, Gisung Sim, Robert Moszynski, Tanya Zelevinsky
History and Philosophy of Physics · Cross-listed from quant-ph
Looking for Work in Quantum Thermodynamics
Eugene Y. S. Chua
This paper diagnoses a much-discussed problem in
quantum thermodynamics, that of generalizing classical work into the
quantum domain. I begin with the no-go
theorem of Perarnau-Llobet et al (2017): no universal measurement scheme for
quantum work satisfies two intuitive, classically consilient desiderata. I assess this incompatibility as stemming from the measurement problem. Decoherence restores compatibility for all practical purposes, but raises questions about what 'universality' should mean and whether any measurement scheme can be 'universal'. I consider a different standard of universality – in terms of ontology – by defining a trajectory-based notion of
quantum work using the
quantum potential. While this preserves the classical role of work as the integral of forces over distances, and evades the tension of the no-go
theorem, consilience fails elsewhere; no single
quantum work concept seems capable of preserving all classical features, raising questions for what it takes for successful generalization of the work concept to
quantum thermodynamics.
Read the full abstract ▾
Fluid Dynamics
Localization of sources in weakly nonlinear fluid systems using linear and quadratic sensitivity analysis
Qi Wang and Zejian You
We develop a framework for localized source detection in dynamical systems governed by nonlinear partial differential equations based on first and second-order sensitivity analysis. Building on the standard adjoint formulation, which relates multiple measurements to external sources through a linear duality relation, we first introduce a linear positional
embedding that identifies the source location by aligning the measurement vector with the
embedding. To capture weakly nonlinear effects that arise when the source intensity is finite, we then incorporate a quadratic correction represented as a symmetric bilinear operator and approximated via a truncated eigen-expansion obtained with Krylov subspace iterations. This yields quadratic positional
embeddings that augment the linear adjoint field, enabling measurement data to be projected onto a higher-dimensional hyperplane, spanned by the linear and quadratic
embeddings. A source search
algorithm is formulated based on principal angle minimization between this hyperplane and the observation vector, providing a natural probabilistic interpretation of source location. The method operates in a one-shot fashion without iterative updates of candidate source positions, and it can be readily extended to scenarios involving multiple sources. Demonstrations on
benchmark inverse problems include perturbation-source identification in the viscous Burgers equation and heat-source detection in a two-dimensional laminar stratified channel. The results with quadratic
embeddings show significant improvements in localization accuracy compared with linear adjoint-based sensitivity methods, especially in the region where linear adjoint sensitivity vanishes.
Read the full abstract ▾
Chemical Physics · Cross-listed from math.CO
Plane partitions and spin adapted quantum states
Abigail Price, Ada Stelzer and Svala Sverrisdóttir
We describe an explicit basis for the $\operatorname{SU}(2)$-invariant space of the exterior power $\wedge_{2k} \mathbb{C}^{2m}$ via the combinatorics of plane partitions. In
quantum chemistry, this is the space of
spin adapted
quantum states of an electronic system with $m$
spin orbitals and $k$ electron pairs. We construct our basis by identifying the invariant space with an Artinian commutative ring called the excitation ring. We compute a Gröbner basis and enumerate its standard monomials via an explicit bijection to Dyck paths counted by the Narayana numbers.
Read the full abstract ▾
Optics
Building blocks of topological band theory for photonic crystals
Yoonseok Hwang, Vaibhav Gupta, Antonio Morales-Pérez et al. (+6 more)
We derive a framework for classifying topological bands in three-dimensional photonic band structures, where the zero frequency polarization singularity implied by Maxwell's equations complicates the direct application of existing
symmetry-based approaches. Building on recent advances in the regularization of photonic bands, we use the recently introduced concept of stable real-space invariants (SRSIs) to show how photonic band structures can be unambiguously characterized in terms of equivalence classes of band representations. We classify topologically trivial photonic bands using SRSIs, treating them as the fundamental building blocks of 3D photonic band structures. This means that if certain bands cannot be constructed from these building blocks, they are necessarily topological. Furthermore, we distinguish between photonic and electronic band structures by analyzing which SRSI values are allowed in systems with and without polarization singularity. We also explore the impact of the polarization singularity on the behavior of Wilson loops, providing new insights into the topological classification of 3D photonic systems.
Read the full abstract ▾
All authors Yoonseok Hwang, Vaibhav Gupta, Antonio Morales-Pérez, Chiara Devescovi, Mikel García-Díez, Juan L. Mañes, Maia G. Vergniory, Aitzol García-Etxarri, Barry Bradlyn
Applied Physics · Cross-listed from cond-mat.stat-mech
Confinement-controlled chase-escape dynamics
R. G. Rossatto, H. Ariel Alvarez, C. Manuel Carlevaro et al. (+1 more)
We investigate a minimal chase-and-escape model on a two-dimensional square
lattice with randomly distributed static obstacles, focusing on how
geometric disorder controls collective pursuit dynamics. Chasers and escapers move according to short-range sensing rules, while the density of obstacles tunes the connectivity of the accessible space. Using a combination of
geometric analysis, dynamical observables, survival statistics, and transport characterization, we establish a direct link between
lattice connectivity and pursuit efficiency. A Breadth-First Search analysis reveals that obstacle-induced fragmentation leads to a progressive loss of accessibility before the percolation threshold, defining the effective initial conditions for the dynamics. The trapping time and capture cost exhibit a non-monotonic dependence on obstacle density, reflecting a competition between path elongation in connected environments and
geometric confinement near the percolation threshold. Survival analysis shows that the decay of the escaper population follows a Weibull form, with characteristic time and shape parameters displaying clear crossovers as a function of obstacle density, signaling the coexistence of cooperative capture and confinement-dominated trapping. Transport properties, quantified through the mean-squared displacement exponent, further support this picture, revealing sub-diffusive dynamics and a convergence toward a geometry-controlled regime near percolation. Overall, our results demonstrate that chase–and–escape dynamics in disordered environments are governed by a geometry-driven crossover, where percolation and connectivity act as unifying control parameters for spatial, temporal, and collective behavior.
Read the full abstract ▾
All authors R. G. Rossatto, H. Ariel Alvarez, C. Manuel Carlevaro, José Rafael Bordin
Physics and Society
Crossing the Functional Desert: Cascade-Driven Assembly and Feasibility Transitions in Early Life
Galen J. Wilkerson
The origin of life poses a problem of combinatorial feasibility: How can temporally supported functional organization arise in exponentially branching assembly spaces when unguided exploration behaves as a memoryless random walk? We show that nonlinear threshold-cascade dynamics in connected interaction networks provide a minimal, substrate-agnostic mechanism that can soften this obstruction. Below a critical connectivity threshold, cascades die out locally and structured input-output response mappings remain sparse and transient-a "functional desert" in which accumulation is dynamically unsupported. Near the critical percolation threshold, system-spanning cascades emerge, enabling discriminative functional responses. We illustrate this transition using a minimal toy model and generalize the argument to arbitrary networked systems. Also near criticality, cascades introduce finite-timescale structural and functional coherence, directional bias, and weak dynamical path-dependence into otherwise memoryless exploration, allowing biased accumulation. This connectivity-driven transition-functional percolation-requires only generic ingredients: interacting units, nonlinear thresholds, influence transmission, and non-zero coherence times. The mechanism does not explain specific biochemical pathways, but it identifies a necessary dynamical regime in which structured functional organization can emerge and be temporarily supported, providing a physical foundation for how combinatorial feasibility barriers can be crossed through network dynamics alone.
Read the full abstract ▾
Fluid Dynamics
Hard Constraint Projection in a Physics Informed Neural Network
Miranda J. S. Horne, Peter K. Jimack, Amirul Khan et al. (+1 more)
In this work, we embed hard constraints in a physics informed neural network (PINN) which predicts solutions to the 2D incompressible Navier Stokes equations. We extend the hard constraint method introduced by Chen et al. (arXiv:2012.06148) from a linear PDE to a strongly non-linear PDE. The PINN is used to estimate the stream function and pressure of the fluid, and by differentiating the stream function we can recover an incompressible velocity field. An unlearnable hard constraint projection (HCP) layer projects the predicted velocity and pressure to a hyperplane that admits only exact solutions to a discretised form of the governing equations.
Read the full abstract ▾
All authors Miranda J. S. Horne, Peter K. Jimack, Amirul Khan, He Wang
Physics Education
Introducing the Physics of Complex Systems through Videogames
Alessio Focardi, Franco Bagnoli, Andrea Guazzini et al. (+1 more)
The purpose of this work is to explore a teaching methodology aimed at communicating topics and subjects not typically studied and analyzed in the (Italian) secondary school. We focused specifically on the use of videogames as a recreational and educational tool, grounding our approach in a broadened conceptual view in which engagement and attentional allocation interact with motivational and affective components of play. Within this perspective, the playful format is considered not only to enhance motivation and enjoyment, but also to attenuate learners' counter-arguing tendencies when confronted with unfamiliar or abstract material. Building on this framework, we developed or adapted several videogames whose central scientific topics are phase transitions, sensitivity to initial conditions, and synchronization. We had a certain number of high school students playing the games, and we asked them several questions to guide them and determine whether the communication was successful. At the end of the activity, we administered a questionnaire about the enjoyment and the difficulties encountered in each game, and the relevant critics.
Read the full abstract ▾
All authors Alessio Focardi, Franco Bagnoli, Andrea Guazzini, Giorgio Gronchi
Optics
Scaleable LED-pumped Room-temperature Maser using a Multi-blade Optical Injector
Mingyang Liu, Zike Cheng, Ziqiu Huang et al. (+3 more)
Though the performance of room-temperature masers has improved over the last decade, relatively little
attention has been paid to the optics used to pump the maser's gain medium. In this work, we investigate a novel multi-blade optical “injector” that permits more effective and more scaleable pumping. The reported work encompasses an interdisciplinary mix of conceptualization, simulation,
crystal growth, fabrication, and microwave engineering. Our gain medium is pentacene dissolved as a solid solution with para-terphenyl (Pc:PTP) molecular
crystal. We accurately determine this pentacene's molecular absorption cross-section as a function of wavelength. Ray-tracing is then used to assess how different designs of waveguide inject light into the Pc:PTP
crystal. A multi-blade injector made of high-refractive-index glass (namely Ohara S-TIH6) is predicted to pump it more completely and uniformly than previous designs. Upon hand-fabricating such an injector and Bridgman-growing a
crystal of 0.1% Pc:PTP over it, an experimental maser oscillator using this combined injector-
crystal assembly is demonstrated. The performance and scaleability of multiblade injection vis-a-vis alternative strategies is analyzed.
Read the full abstract ▾
All authors Mingyang Liu, Zike Cheng, Ziqiu Huang, Yifan Yu, Michael Newns, Mark Oxborrow
Chemical Physics
Rotational Coherence Dominates Early-Time Dynamics and Produces Long-Time Revivals in the S2 State of Azulene
Jie Zhan, Alexander K. Lemmens, Musahid Ahmed et al. (+1 more)
The ultrafast dynamics of azulene have been debated for decades, with reported picosecond decay constants variously attributed to intramolecular vibrational redistribution (IVR), internal conversion, or rotational dephasing. Using polarization and femtosecond time-resolved Resonance Enhanced Multi-
photon Ionization Spectroscopy with a nanosecond delay window, we disentangle this long-standing inconsistency and show that the early 2-5 ps decay component arises entirely from rotational dephasing of an excited-state wavepacket. Identical time constants extracted from the decay of the parallel signal and rise of the perpendicular signal across multiple vibronic origins provide an unambiguous rotational anisotropy signature, eliminating the need for IVR-based interpretations. Extending the measurement window to 1.3 ns reveals well-structured J-type and C-type rotational coherence revivals in S2 azulene on top of the well-documented fluorescence decay, demonstrating that both the short- and long-time dynamics contain information about the coherent rotational dynamics. These results show that azulene, and by extension polycyclic aromatic hydrocarbons (PAH), can sustain structured rotational coherence deep into the nanosecond regime, positioning PAHs as model systems for
quantum-coherent wavepacket dynamics and providing a framework for probing coherence, decoherence, and rotational control in electronically rich molecular systems.
Read the full abstract ▾
All authors Jie Zhan, Alexander K. Lemmens, Musahid Ahmed, Melanie A. R. Reber